Solving the enigma of weak fluorine contacts in the solid state: A periodic DFT study of fluorinated organic crystals

Abstract

The nature and strength of weak interactions with organic fluorine in the solid state are revealed by periodic density functional theory (periodic DFT) calculations coupled with experimental data on the structure and sublimation thermodynamics of crystalline organofluorine compounds. To minimize other intermolecular interactions, several sets of crystals of perfluorinated and partially fluorinated organic molecules are considered. This allows us to establish the theoretical levels providing an adequate description of the metric and electron-density parameters of the C-F⋯F-C interactions and the sublimation enthalpy of crystalline perfluorinated compounds. A detailed comparison of the C-F⋯F-C and C-H⋯F-C interactions is performed using the relaxed molecular geometry in the studied crystals. The change in the crystalline packing of aromatic compounds during their partial fluorination points to the structure-directing role of C-H⋯F-C interactions due to the dominant electrostatic contribution to these contacts. C-H⋯F-C and C-H⋯O interactions are found to be identical in nature and comparable in energy. The factors that determine the contribution of these interactions to the crystal packing are revealed. The reliability of the results is confirmed by considering the superposition of the electrostatic potential and electron density gradient fields in the area of the investigated intermolecular interactions.